TW201631206A - 鍍敷前處理方法、鍍敷處理系統及記憶媒體 - Google Patents
鍍敷前處理方法、鍍敷處理系統及記憶媒體 Download PDFInfo
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- TW201631206A TW201631206A TW104121488A TW104121488A TW201631206A TW 201631206 A TW201631206 A TW 201631206A TW 104121488 A TW104121488 A TW 104121488A TW 104121488 A TW104121488 A TW 104121488A TW 201631206 A TW201631206 A TW 201631206A
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- Prior art keywords
- catalyst
- layer
- substrate
- plating
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- 238000007747 plating Methods 0.000 title claims abstract description 146
- 238000002203 pretreatment Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 290
- 239000000758 substrate Substances 0.000 claims abstract description 179
- 238000000034 method Methods 0.000 claims abstract description 58
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims description 346
- 238000010438 heat treatment Methods 0.000 claims description 39
- 230000004888 barrier function Effects 0.000 claims description 14
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004590 computer program Methods 0.000 claims description 4
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000010949 copper Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 46
- 239000007788 liquid Substances 0.000 description 31
- 230000007246 mechanism Effects 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 239000002105 nanoparticle Substances 0.000 description 19
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- 230000006870 function Effects 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000009623 Bosch process Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76874—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroless plating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1632—Features specific for the apparatus, e.g. layout of cells and of its equipment, multiple cells
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76843—Barrier, adhesion or liner layers formed in openings in a dielectric
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76853—Barrier, adhesion or liner layers characterized by particular after-treatment steps
- H01L21/76861—Post-treatment or after-treatment not introducing additional chemical elements into the layer
- H01L21/76864—Thermal treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76898—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics formed through a semiconductor substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
- C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemically Coating (AREA)
- Electrodes Of Semiconductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Thermal Sciences (AREA)
Abstract
提供一種觸媒層不會對基板剝離的鍍敷前處理方法。
對基板形成觸媒層的鍍敷前處理方法,係具備有:使觸媒(22a)吸附於基板(2)上,而形成觸媒層(22)的工程;及在觸媒層(22)的正上方形成觸媒固定層(27)的工程。
Description
本發明,係關於對基板形成觸媒層之鍍敷前處理方法、鍍敷處理系統及記憶媒體。
近年來,LSI等的半導體裝置,係對應於實裝面積之省空間化或改善處理速度這樣的課題,追求更進一步高密度化。作為實現高密度化之技術的一例,已知有藉由層積複數個配線基板的方式來製作三次元LSI等之多層基板的多層配線技術。
在多層配線技術中,一般而言為了確保配線基板間之導通,而在配線基板設置貫通配線基板並且填埋有銅(Cu)等之導電性材料的貫通導孔。作為用以製作填埋有導電性材料之貫通導孔之技術的一例,已知有無電解鍍敷法。
作為製作配線基板的具體方法,已知下述方法:準備形成有凹部的基板,接著,在基板的凹部內形成作為Cu擴散防止膜之阻障膜,且藉由無電解Cu鍍敷而在該阻障膜上形成種膜。之後,藉由電解Cu鍍敷而在凹
部內填埋有Cu,填埋有Cu的基板,係藉由化學機械研磨等的研磨方法來予以薄膜化,藉此,製作具有貫通導孔(該貫通導孔,係填埋有Cu)的配線基板。
在上述配線基板中形成阻障膜的情況下,預先使觸媒吸附於基板而形成觸媒層,且可藉由對該觸媒層上施予鍍敷處理的方式,得到阻障膜。阻障膜,係之後被燒固而去除內部的水分,且強化金屬間結合。
另外,在使觸媒吸附於基板的情況下,開發一種使用鈀等之奈米粒子來作為觸媒的技術。
[專利文獻1]日本特開2013-67856號公報
如上述,在使觸媒吸附於基板的情況下,開發了一種使用鈀等之奈米粒子來作為觸媒的技術,此時,為了使觸媒吸附,有一種情形是在基板上預先形成密接層。
然而,即使預先在基板上形成密接層,亦存在有下述情形:當鍍敷層之厚度變厚,則鈀之奈米粒子會從密接層剝落,在該情況下,則難以精度良好地形成鍍敷
層。
本發明,係考慮像這樣之觀點而進行研究者,以提供一種可形成有觸媒層(該觸媒層,係使得以在基板上進行鍍敷處理的前處理而形成的觸媒不會從基板剝落)的鍍敷前處理方法、鍍敷處理系統及記憶媒體為目的。
本發明,係一種鍍敷前處理方法,其特徵係,具備有:準備基板的工程;使觸媒吸附於前述基板上而形成觸媒層的工程;及在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於前述基板)的工程。
本發明,係一種鍍敷處理系統,其特徵係,具備有:觸媒層形成部,使觸媒吸附於基板上,而形成觸媒層;層形成部,在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於基板);及基板搬送部,在前述觸媒層形成部與前述觸媒固定層形成部之間搬送基板。
本發明,係一種記憶媒體,儲存有電腦程式(該電腦程式,係用以使鍍敷前處理方法執行於鍍敷處理
系統),該記憶媒體,其特徵係,前述鍍敷前處理方法,係具備有:準備基板的工程;使觸媒吸附於前述基板上而形成觸媒層的工程;及在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於前述基板)的工程。
根據本發明,由於設置有觸媒固定層(該觸媒固定層,係固定形成於基板上的觸媒),因此,觸媒不會從基板剝落。因此,藉由後製程所形成的鍍敷層亦不會從基板剝落。
2‧‧‧基板
2A‧‧‧TEOS層
2a‧‧‧凹部
10‧‧‧鍍敷處理系統
11‧‧‧基板搬送臂
12‧‧‧密接層形成部
13‧‧‧觸媒層形成部
14‧‧‧鍍敷層形成部
15‧‧‧加熱部
16‧‧‧無電解Cu鍍敷層形成部
17‧‧‧電解Cu鍍敷層形成部
18‧‧‧卡匣站
19‧‧‧控制部
19A‧‧‧記憶媒體
20‧‧‧觸媒固定層形成部
21‧‧‧密接層
21a‧‧‧SAM層
21b‧‧‧TPT層
22‧‧‧觸媒層
22a‧‧‧觸媒
23‧‧‧鍍敷層
24‧‧‧無電解Cu鍍敷層
25‧‧‧電解Cu鍍敷層
27‧‧‧觸媒固定層
[圖1]圖1,係表示本發明之實施形態之鍍敷處理系統全體的方塊圖。
[圖2]圖2,係表示組入有本發明之實施形態之鍍敷前處理方法之鍍敷處理方法全體的流程圖。
[圖3]圖3(a)~(g),係表示施予鍍敷處理方法之基板的圖。
[圖4]圖4(a)(b),係表示本發明之實施形態之形成於基板上之觸媒層及觸媒固定層的剖面圖。
[圖5]圖5(a)(b),係表示作為比較例之形成於
基板上之觸媒層的側剖面圖。
[圖6]圖6(a)(b),係表示本發明之實施形態之形成於基板上之觸媒層、觸媒固定層及鍍敷層的側剖面圖。
[圖7]圖7(a)(b),係表示作為比較例之形成於基板上之觸媒層及鍍敷層的側剖面圖。
[圖8]圖8,係表示觸媒層形成部的側剖面圖。
[圖9]圖9,係表示觸媒層形成部的平面圖。
[圖10]圖10,係表示第1加熱部及第2加熱部的圖。
藉由圖1~圖10來說明本發明之一實施形態。
首先,藉由圖1來敘述本發明之鍍敷處理系統全體。
如圖1所示,鍍敷處理系統10,係對半導體晶圓等之具有凹部2a的基板(矽基板)2施予鍍敷處理者(參閱圖3(a)~(g))。在該情況下,在矽基板2上預先施予TEOS處理,而形成有TEOS層2A(參閱圖4(a)(b))。
像這樣的鍍敷處理系統10,係具備有:卡匣站18,載置有收容了基板2的卡匣(未圖示);基板搬
送臂11,從卡匣站18之卡匣取出基板2並進行搬送;及基板搬送臂11進行行走的行走路徑11a。
又,在行走路徑11之一側,配置有:密接層形成部12,使矽烷耦合劑等之耦合劑吸附於基板2上,而形成後述之密接層21;觸媒層形成部13,使觸媒22a吸附於基板2的密接層21上,而形成後述之觸媒層22;及鍍敷層形成部14,在基板2之觸媒層22上,形成具有後述之Cu擴散防止膜(阻障膜)之功能的鍍敷層23。又,設置有:觸媒固定層形成部20,其係鄰接於觸媒層形成部13,且在觸媒層22上設置觸媒固定層27,藉由該觸媒固定層27來使觸媒層22固定於基板2之TEOS層2A上)。
又,在行走路徑11的另一側,配置有:加熱部15,燒固形成於基板2的觸媒層22、觸媒固定層27及鍍敷層23;及無電解Cu鍍敷層形成部16,用以在形成於基板2的鍍敷層23上,形成具有後述之種膜之功能的無電解銅鍍敷層(無電解Cu鍍敷層)24。
又,配置有:電解Cu鍍敷層形成部17,其係鄰接於加熱部15,且用以在形成於基板2的凹部2a內,以無電解Cu鍍敷層24作為種膜而充填電解銅鍍敷層(電解Cu鍍敷層)25。
另外,加熱部15,係如上述具有燒固觸媒固定層27之第1加熱部的功能,並且具有燒固觸媒層22之第2加熱部的功能。又,可藉由在加熱部15中加熱形成
有鍍敷層23之基板2的方式,燒固鍍敷層23。
又,觸媒層22之觸媒22a,係在形成鍍敷層23之際,發揮觸媒功能者,觸媒固定層27,係將觸媒層22固定於基板2者。
又,上述之鍍敷處理系統的各構成構件,例如卡匣站18、基板搬送臂11、密接層形成部12、觸媒層形成部13、觸媒固定層形成部20、鍍敷層形成部14、加熱部15、無電解Cu鍍敷層形成部16及電解Cu鍍敷層形成部17,皆係根據記錄於記憶媒體19A(該記憶媒體,係設置於控制部19)的各種程式,以控制部19來驅動控制,藉由此,對基板2進行各種處理。在此,記憶媒體19A,係儲存有各種設定資訊或後述之鍍敷處理程式等的各種程式。作為記憶媒體19A,係可使用電腦可讀取之ROM或RAM等之記憶體或硬碟、CD-ROM、DVD-ROM或軟碟片等之碟片狀記憶媒體等之習知者。
接下來,進一步敍述用以形成觸媒層22的觸媒層形成部13。
觸媒層形成部13,係可由圖8及圖9所示的液處理裝置來構成。
另外,鍍敷層形成部14及無電解Cu鍍敷層形成部16,係亦可由與觸媒層形成部13同樣的液處理裝置來構成。觸媒層形成部13,係如圖8及圖9所示者。
亦即,觸媒層形成部13,係如圖8及圖9所示,具備有:基板旋轉保持機構(基板收容部)110,用
以在殼體101之內部旋轉保持基板2;液供給機構30,90,對基板2之表面供給觸媒溶液或洗淨液等;罩杯105,承接從基板2所飛散之觸媒溶液或洗淨液等;排出口124,129,134,排出以罩杯105所承接的觸媒溶液或洗淨液;液排出機構120,125,130,排出在排出口所收集的液體;及控制機構160,控制基板旋轉保持機構110、液供給機構30,90、罩杯105及液排出機構120,125,130。
其中,基板旋轉保持機構110,係如圖8及圖9所示,具有:中空圓筒狀之旋轉軸111,在殼體101內上下延伸;旋轉台112,被安裝於旋轉軸111之上端部;晶圓夾具113,設置於旋轉台112之上面外周部且支撐基板2;及旋轉機構162,旋轉驅動旋轉軸111。其中,旋轉機構162,係藉由控制機構160來控制,且藉由旋轉機構162使旋轉軸111旋轉驅動,藉由此,使藉由晶圓夾具113所支撐的基板2旋轉。
接下來,參閱圖8及圖9,說明對基板2之表面供給觸媒溶液或洗淨液等的液供給機構30,90。液供給機構30,90,係包含有:觸媒溶液供給機構30,對基板2之表面供給觸媒溶液;及洗淨液供給機構90,對基板2之表面供給洗淨液。
如圖8及圖9所示,吐出噴嘴32,係被安裝於噴嘴頭104。又,噴嘴頭104,係被安裝於臂部103之前端部,該臂部103,係可上下方向延伸,且被固定於藉
由旋轉機構165來旋轉驅動的支撐軸102。觸媒溶液供給機構30之觸媒溶液供給管33,係配置於臂部103之內側。藉由像這樣的構成,可使觸媒溶液經由吐出噴嘴32,從所要的高度吐出至基板2之表面的任意部位。
洗淨液供給機構90,係如後述使用於基板2的洗淨工程者,如圖8所示,包含有被安裝於噴嘴頭104的噴嘴92。在該情況下,從噴嘴92,選擇性地將洗淨液或沖洗處理液之任一吐出至基板2之表面。
接下來,參閱圖8,說明排出從基板2飛散之觸媒溶液或洗淨液等的液排出機構120,125,130。如圖8所示,在殼體101內,係配置有罩杯105(該罩杯,係藉由升降機構164驅動於上下方向,且具有排出口124,129,134)。液排出機構120,125,130,係排出分別在排出口124,129,134所收集的液體者。
如圖8所示,鍍敷液排出機構120,125,係分別具有藉由流路切換器121,126切換的回收流路122,127及廢棄流路123,128。其中回收流路122,127,係用以回收觸媒溶液而進行再利用的流路,另一方面,廢棄流路123,128,係用以廢棄觸媒溶液的流路。另外,如圖8所示,在處理液排出機構130,係僅設置有廢棄流路133。
又,如圖8及圖9所示,在基板收容部110之出口側,係連接有排出觸媒溶液之觸媒溶液排出機構120的回收流路122,該回收流路122中之在基板收容部
110的出口側附近,設置有冷卻觸媒溶液的冷卻緩衝器120A。
接下來,敘述觸媒固定層形成部20。觸媒固定層形成部20,係由噴霧式的塗佈裝置(該噴霧式的塗佈裝置,係對基板2上噴露觸媒固定層形成用材料而進行塗佈)所構成,且可在基板2之觸媒層22上形成觸媒固定層27。
另外,作為觸媒固定層形成部20,亦可使用其他如圖8及圖9所示的液處理裝置,且在該情況下,可將噴嘴頭104固定於基板2之中心,一邊使基板2旋轉,一邊從噴嘴頭104對基板2上供給觸媒固定層形成用材料。
或者,作為觸媒固定層形成部20,係亦可使用圖8及圖9所示之液處理裝置,並且使用開縫式的噴嘴來代替噴嘴頭104。如此一來,在使用開縫式的噴嘴時,亦可不使基板2在液處理裝置內旋轉並使其停止,而使開縫式的噴嘴在基板2上旋動。
接下來,敘述加熱部15。
加熱部15,係如圖10所示,具備有密閉的密閉殼體15a與加熱板15A(該加熱板,係配置於密閉殼體15a內部)。
在鍍敷層燒固部15之密閉殼體15a,係設置有用以搬送基板2之搬送口(未圖示),又,在密閉殼體15a內,係從N2氣體供給口15c供給有N2氣體。
同時地,密閉殼體15a內,係藉由排氣口15b予以排氣,且可藉由使密閉殼體15a內充滿N2氣體的方式,使密閉殼體15a內保持為惰性環境。
接下來,藉由圖2~圖7,說明由像這樣之構成所形成的本實施形態的作用。
首先,在前工程中,對由半導體晶圓等所構成的基板(矽基板)2形成凹部2a,並且之後在基板2上形成TEOS層2A。接下來,形成有TEOS層2A的基板2,係被搬送至鍍敷處理系統10內。
而且,在鍍敷處理系統10之密接層形成部12內,在具有凹部2a之基板2的TEOS層2A上形成有密接層21(圖2及圖3(a))。
在此,作為在基板2形成凹部2a的方法,係可適當地採用以往習知的方法。具體而言,例如作為乾蝕刻技術,可適用使用了氟系或氯系氣體等之泛用的技術,特別是要形成深寬比(孔的深度/孔徑)較大的孔時,更可適切地採用使用了可以高速進行深蝕刻之ICP-RIE(Inductively Coupled Plasma Reactive Ion Etching:感應耦合電漿-反應性離子蝕刻)之技術的方法,特別是,可適切地採用被稱為博希製程(bosch process)的方法,該博希製程,係反覆進行使用了六氟化硫(SF6)的蝕刻步驟與使用了C4F8等之鐵氟龍系氣體的保護步驟。
又,密接層形成部12,係具有真空室(未圖示)(該真空室,係具有加熱部),在該密接層形成部12內,矽烷耦合劑等的耦合劑,係被吸附於具有凹部2a的基板2上,如此一來,在基板2的TEOS層2A上形成有密接層21(SAM處理)。使吸附矽烷耦合劑而形成的密接層21,係提高後述之觸媒層22與基板2的密接性者,且由SAM層21a所構成(參閱圖4(a))。
另外,如圖4(b)所示,亦可在SAM層21a上塗佈包含有氧化鈦劑的鈦酸鹽劑,而設置鈦酸鹽系之密接層(TPT層)21b,且藉由SAM層21a與TPT層21b來形成密接層21。或者,亦可在基板2之TEOS層2A上設置鈦酸鹽系之密接層(TPT層)21b,且僅藉由該TPT層21b來形成密接層21。
在密接層形成部12中,形成有密接層21的基板2,係藉由基板搬送臂11,被傳送至觸媒層形成部13(該觸媒層形成部,係由圖8及圖9所示的液處理裝置所構成)。而且,在該觸媒層形成部13中,例如形成為觸媒22a的奈米鈀(nano palladium),係吸附於基板2之密接層21上,而形成觸媒層22(圖3(b))。
具體而言,在圖8及圖9所示的觸媒層形成部13中,藉由使包含有觸媒22a的觸媒溶液從噴嘴頭104之吐出噴嘴32噴出至基板2上的方式,使觸媒22a吸附於基板2之密接層21上,如此一來,可形成觸媒層27。而且,基板2上之多餘的觸媒溶液,係可藉由從噴嘴
頭104之噴嘴92噴出洗淨液的方式來除去。
接下來,說明供給至基板2之觸媒溶液及包含於觸媒溶液的觸媒22a。一開始,說明觸媒22a。
作為被吸附於基板2之密接層21的觸媒22a,係適切地使用具有可促進鍍敷反應之觸媒作用的觸媒,例如使用由奈米粒子所構成的觸媒。在此,奈米粒子,係指具有觸媒作用之膠體狀的粒子,且平均粒徑為20nm以下,例如為0.5nm~20nm之範圍內的粒子。作為構成奈米粒子的元素,係例如可列舉出鈀、金、白金等。其中,可將奈米粒子之鈀表示為n-Pd。
又,作為構成奈米粒子的元素,亦可使用釕。
測定奈米粒子之平均粒徑的方法並不特別限定,可使用各種方法。例如,在測定觸媒溶液內之奈米粒子的平均粒徑時,可使用動態光散射法等。動態光散射法,係指對分散於觸媒溶液內的奈米粒子照射雷射光,藉由觀察其散亂光的方式來計算奈米粒子之平均粒徑等的方法。又,在測定吸附於基板2之凹部2a之奈米粒子的平均粒徑的情況下,亦可從使用TEM或SEM等所獲得的圖像,來檢測預定個數的奈米粒子,例如20個奈米粒子,從而計算該些奈米粒子之粒徑的平均值。
接下來,說明包含有由奈米粒子所構成之觸媒的觸媒溶液。觸媒溶液,係指含有構成形成為觸媒之奈米粒子之金屬的離子者。在例如奈米粒子是由鈀所構成的
情況下,在觸媒溶液中,係以含有氯化鈀等的鈀化合物來作為鈀離子源。
觸媒溶液的具體組成並不特別限定,但較佳的是以使得觸媒溶液之黏性係數成為0.01Pa.s以下的方式,設定觸媒溶液的組成。藉由將觸媒溶液之黏性係數設成為上述範圍內的方式,即使基板2之凹部2a的直徑小,還是可使觸媒溶液充分地滲透至基板2之凹部2a的下部。藉此,可使觸媒22a更確實地吸附至基板2之凹部2a的下部。
最好,觸媒溶液中的觸媒22a,係藉由分散劑來被覆。藉此,可縮小觸媒22a之界面的界面能量。因此,可更促進觸媒溶液內之觸媒22a的擴散,藉此,可使觸媒22a以更短時間到達基板2之凹部2a的下部。又,可防止複數個觸媒22a凝集而其粒徑變大,藉此亦可更促進觸媒溶液內之觸媒22a的擴散。
準備以分散劑所被覆之觸媒22a的方法並不特別限定。例如,亦可預先對觸媒層形成部13供給包含有以分散劑所被覆之觸媒22a的觸媒溶液。或者,亦可以在觸媒層形成部13的內部,例如在觸媒溶液供給機構30實施由分散劑來被覆觸媒22a之工程的方式,構成觸媒層形成部13。
具體而言,作為分散劑,係聚乙烯吡咯烷酮(PVP)、聚丙烯酸(PAA)、聚乙烯亞胺(PEI)、四甲基銨(TMA)、檸檬酸等為較佳。
其他,用以調整特性的各種藥劑亦可被添加於觸媒溶液。
另外,作為包含有觸媒22a的觸媒溶液,係不限於包含有n-Pd等之奈米粒子的觸媒溶液,亦可使用氯化鈀水溶液(PdCl2)來作為觸媒溶液,且使用氯化鈀(PdCl2)中的Pd離子來作為觸媒22a。
如此一來,在觸媒層形成部13中,在基板2之密接層21上形成觸媒層22之後,基板2,係藉由基板搬送臂11被傳送至加熱部15,在該加熱部15中,基板2被加熱,且觸媒層22被燒固(Bake處理)。在該情況下,在加熱部15之密閉殼體15a內,於N2氣體環境中,基板2,係在例如150℃~250℃的溫度範圍下,於加熱板15A上被加熱10~30分鐘,使得觸媒層22被加熱而燒固。另外,該觸媒層22之燒固工程並非必需者。
接下來,形成有觸媒層22且觸媒層22被燒固的基板2,係藉由基板搬送臂11被傳送至觸媒固定層形成部20。接下來,在觸媒固定層形成部20中,從例如噴霧式之塗佈裝置,對基板2之觸媒層22上塗佈觸媒固定層形成用材料,而在觸媒層22上形成觸媒固定層27(參閱圖3(c))。
作為觸媒固定層形成用材料,係可使用例如有機絕緣性材料(SOG、Low-k)或無機絕緣性材料(Si-O-C)。
形成於觸媒層22上的觸媒固定層27,係將包
含有觸媒22a的觸媒層22固定於基板2的密接層21上,且可藉由觸媒固定層27來防止吸附於密接層21的觸媒22a剝離。
在該情況下,觸媒固定層27的平均厚度,係形成為觸媒22a的平均粒徑×0.2~1.0。
當觸媒固定層27之平均厚度小於觸媒22a的平均粒徑×0.2時,則難以藉由觸媒固定層27來將觸媒層22堅固地固定於基板2。另一方面,當觸媒固定層27之平均厚度大於觸媒22a的平均粒徑×1.0時,則無法使觸媒22a從觸媒固定層27露出於上方,且在後製程中,無法在鍍敷處理中發揮作為觸媒的效果。
因此,觸媒固定層27之平均厚度,係設定為如上述般之範圍。
如此一來,在觸媒固定層形成部20中,在基板2的觸媒層22上形成觸媒固定層27之後,基板2,係藉由基板搬送臂11被傳送至加熱部15,在該加熱部15之密閉殼體15a內,於N2氣體環境中,基板2,係在加熱板15A上被加熱,而觸媒固定層27被燒固(Bake處理)。在該情況下,在加熱部15中,基板2,係在例如150℃~250℃的溫度範圍下,被加熱10~30分鐘,使得觸媒固定層27被加熱而燒固。
另外,在用以形成觸媒固定層27之觸媒固定層形成用材料為包含有溶劑的情況下,事先在加熱部15內充分地進行加熱,從而完全去除觸媒固定層27中的溶
劑為較佳。
可藉由像這樣所形成的觸媒層22與將該觸媒層22固定的觸媒固定層27,來得到觸媒層22A。
如此一來,由於是根據本實施形態,使觸媒22a吸附於密接層21上(該密接層,係由形成於基板2之TEOS2A的SAM層21a所構成),而形成觸媒層22,而且在觸媒層22上形成觸媒固定層27,因此,可藉由該觸媒固定層27來將觸媒22確實地固定於基板2上(參閱圖4(a))。
對此,亦考慮如圖5(a)所示之比較例,在觸媒層22上不設置觸媒固定層27的情況下,如後述,在觸媒層22上形成鍍敷層23後時,在密接層21與觸媒層22的界面中會產生層間剝離。
對此,由於根據本實施形態,觸媒層22,係藉由觸媒固定層27被固定於基板2,因此,在密接層21與觸媒層22的界面中,不會產生層間剝離。
又,由於是根據本實施形態,使觸媒22a吸附於密接層21上(該密接層,係由形成於基板2之TEOS2A的SAM層21a與TPT層21b所構成),而形成觸媒層22,而且在觸媒層22上形成觸媒固定層27,因此,可藉由該觸媒固定層27來將觸媒22確實地固定於基板2上(參閱圖4(b))。
對此,亦考慮如圖5(b)所示之比較例,在觸媒層22上不設置觸媒固定層27的情況下,如後述,在
觸媒層22上形成鍍敷層23時,在密接層21與觸媒層22的界面中會產生層間剝離。
對此,由於根據本實施形態,觸媒層22,係藉由觸媒固定層27被固定於基板2,因此,在密接層21與觸媒層22的界面中,不會產生層間剝離。
如此一來,在觸媒固定層形成部20中,在基板2上形成觸媒固定層27之後,基板2,係藉由基板搬送臂11被傳送至鍍敷層形成部14。
接下來,在鍍敷層形成部14中,在基板2之觸媒層22上,形成有鍍敷層23(該鍍敷層,係具有Cu擴散防止膜(阻障膜)的功能)(圖3(d))。
在該情況下,鍍敷層形成部14,係由如圖8及圖9所示的液處理裝置所構成,且可藉由對基板2之觸媒層22上施予無電解鍍敷處理的方式,形成鍍敷層23。
在鍍敷層形成部14中形成鍍敷層23的情況下,作為鍍敷液,係可使用包含有例如Co-W-B的鍍敷液,且鍍敷液之溫度,係維持為40~75℃(較佳係65℃)。
藉由對基板2上供給包含有Co-W-B之鍍敷液的方式,在基板2之觸媒層22上,藉由無電解鍍敷處理來形成包含有Co-W-B的鍍敷層23。
接下來,基板2(該基板,係在觸媒層22上形成有鍍敷層23),係藉由基板搬送臂11,從鍍敷層形成部14被傳送至加熱部15的密閉殼體15a內。而且,在
該鍍敷層燒固部15的密閉殼體15a內,基板2,係於N2氣體環境中,在加熱板15A上被加熱。如此一來,基板2之鍍敷層23被燒固(Bake處理)。
在加熱部15中,燒固鍍敷層23之際的燒固溫度,係150~200℃,燒固時間,係10~30分鐘。
如此一來,可藉由燒固基板2上之鍍敷層23的方式,使鍍敷層23內的水分往外放出,且可同時提高鍍敷層23內的金屬間結合。
像這樣形成的鍍敷層23,係具有Cu擴散防止層(阻障膜)的功能。接下來,基板2(該基板,係形成有具有阻障膜之功能的鍍敷層23),係之後藉由基板搬送臂11被傳送至無電解Cu鍍敷層形成部16。
接下來,在無電解Cu鍍敷層形成部16中,在基板2之鍍敷層層積體23上,形成有無電解Cu鍍敷層24(圖3(e))(該無電解Cu鍍敷層,係具有用以形成電解Cu鍍敷層25之種膜的功能)。
在該情況下,無電解Cu鍍敷層形成部16,係由如圖8及圖9所示的液處理裝置所構成,且可藉由對基板2之鍍敷層23上施予無電解鍍敷處理的方式,形成無電解Cu鍍敷層24。
在無電解Cu鍍敷層形成部16所形成的無電解Cu鍍敷層24,係具有用以形成電解Cu鍍敷層25之種膜的功能,在無電解Cu鍍敷層形成部16所使用的鍍敷液中,係含有成為銅離子源的銅鹽,例如硫酸銅、硝酸銅、
氯化銅、溴化銅、氧化銅、氫氧化銅、焦磷酸銅等。又,在鍍敷液中,係更含有銅離子的錯合劑及還原劑。又,在鍍敷液中,係亦可含有用以使鍍敷反應之穩定性或速度提升的各種添加劑。
如此一來,形成有無電解Cu鍍敷層24的基板2,係藉由基板搬送臂11被傳送至電解Cu鍍敷層形成部17。另外,亦可在將形成有無電解Cu鍍敷層24的基板2傳送至加熱部15並燒固之後,傳送至電解Cu鍍敷層形成部17。接下來,在電解Cu鍍敷層形成部17中,對基板2施予電解Cu鍍敷處理,在基板2之凹部2a內,將無電解Cu鍍敷層24作為種膜充填電解Cu鍍敷層25(圖3(f))。
之後,基板2,係從鍍敷處理系統10往外排出,基板2的背面側(與凹部2a相反之側)被化學機械研磨(圖3(g))。
另外,在上述實施例中,雖係表示以電解Cu鍍敷處理來充填電解Cu鍍敷層的例子,但不限於此,亦可以無電解Cu鍍敷處理來代替電解Cu鍍敷處理,形成Cu鍍敷層。
又,在上述實施例中,雖係表示在加熱基板2的情況下,在加熱部15之密閉殼體15a內,於充填有N2氣體的惰性環境中,在加熱板15A上加熱基板2的例子,但不限於此,亦可將例如低溫化或縮短處理時間作為目的,使密閉殼體15a內成為真空,而在加熱板15A上加熱
基板2。
又,在上述實施例中,雖係表示分別以單獨的裝置來進行觸媒層形成部13與加熱部15的例子,但不限於此,亦可在圖8所示的觸媒層形成部13中,在基板2之上方設置燈照射部200(UV光等)或覆蓋基板2之加熱板(未圖示)等的加熱源,而在觸媒層形成部13內進行觸媒層之燒固。而且,雖表示在基板2之觸媒層22上形成具有Cu擴散防止層(阻障層)之功能之鍍敷層23的例子,但亦可在作為阻障層的鍍敷層23上形成觸媒層22,並在該觸媒層22上形成具有種膜之功能的無電解Cu鍍敷層24。
接下來,藉由圖6(a)(b)及圖7(a)(b)來說明本發明的具體實施例。如圖6(a)(b)所示,在基板2之TEOS2A上形成由SAM層21a所構成的密接層21,使由n-Pd所構成的觸媒22a吸附於該密接層21上,而形成觸媒層22。接下來,在觸媒層22上形成觸媒固定層27,將觸媒層22固定於基板2之密接層21上,進一步使用觸媒層22的觸媒22a,形成由CoWB膜所構成的鍍敷層23。
接下來,將膠帶黏貼於該鍍敷層23並實施剝
離的Tape Test之後,在鍍敷層23中並未看到剝離部分。
接下來,作為比較例,如圖7(a)(b)所示,在基板2之TEOS2A上形成由SAM層21a所構成的密接層21,使由n-Pd所構成的觸媒22a吸附於該密接層21上,而形成觸媒層22。接下來,在觸媒層22上不形成觸媒固定層27,而使用觸媒層22的觸媒22a,形成由CoWB膜所構成的鍍敷層23。
接下來,將膠帶黏貼於該鍍敷層23並實施剝離的Tape Test之後,在鍍敷層23中發現剝離部分23A。
該鍍敷層23之剝離部分23A,係在密接層21與觸媒層22的界面中產生剝離,且因剝離(該剝離,係在該密接層21與觸媒層22的界面中產生)而產生者。
Claims (14)
- 一種鍍敷前處理方法,其特徵係,具備有:準備基板的工程;使觸媒吸附於前述基板上而形成觸媒層的工程;及在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於前述基板)的工程。
- 如申請專利範圍第1項之鍍敷前處理方法,其中,前述觸媒固定層之平均厚度,係設定為至少前述觸媒之上部露出的範圍。
- 如申請專利範圍第1項之鍍敷前處理方法,其中,在形成前述觸媒層之前,以鄰接於前述觸媒層的方式,在前述基板上預先形成密接層。
- 如申請專利範圍第3項之鍍敷前處理方法,其中,前述密接層,係由下述者所構成:矽烷耦合劑所致之密接層或鈦酸鹽劑所致之密接層、或矽烷耦合劑所致之密接層與鈦酸鹽劑所致之密接層的層積體。
- 如申請專利範圍第1項之鍍敷前處理方法,其中,在形成前述觸媒層之前,以鄰接於前述觸媒層的方式,在前述基板上預先形成阻障層。
- 如申請專利範圍第1項之鍍敷前處理方法,其 中,更具備:在形成前述觸媒固定層之後,加熱前述基板而燒固前述觸媒固定層的工程。
- 如申請專利範圍第6項之鍍敷前處理方法,其中,更具備有:在形成前述觸媒固定層之前,加熱前述基板而燒固前述觸媒層的工程。
- 一種鍍敷處理系統,其特徵係,具備有:觸媒層形成部,使觸媒吸附於基板上,而形成觸媒層;層形成部,在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於基板);及基板搬送部,在前述觸媒層形成部與前述觸媒固定層形成部之間搬送基板。
- 如申請專利範圍第8項之鍍敷處理系統,其中,前述觸媒固定層形成部,係前述觸媒固定層之平均厚度設定為至少前述觸媒之上部露出的範圍。
- 如申請專利範圍第8項之鍍敷處理系統,其中,設置有:密接層形成部,其係在前述基板上形成密接層。
- 如申請專利範圍第8項之鍍敷處理系統,其中,設置有:阻障層形成部,其係在前述基板上形成阻障層。
- 如申請專利範圍第8項之鍍敷處理系統,其中, 更設置有:第1加熱部,其係加熱前述基板,而燒固前述上塗層。
- 如申請專利範圍第8項之鍍敷處理系統,其中,更設置有:第2加熱部,其係加熱前述基板,而燒固前述觸媒吸附層。
- 一種記憶媒體,係儲存有電腦程式(該電腦程式,係用以使鍍敷前處理方法執行於鍍敷處理系統),該記憶媒體,其特徵係,前述鍍敷前處理方法,係具備有:準備基板的工程;使觸媒吸附於前述基板上而形成觸媒層的工程;及在前述觸媒層上設置觸媒固定層(該觸媒固定層,係將前述觸媒固定於前述基板)的工程。
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JP7241594B2 (ja) * | 2019-04-22 | 2023-03-17 | 東京エレクトロン株式会社 | 基板処理方法および基板処理装置 |
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JPH05218020A (ja) * | 1992-01-31 | 1993-08-27 | Nec Corp | 薄膜配線の形成方法 |
US5824599A (en) * | 1996-01-16 | 1998-10-20 | Cornell Research Foundation, Inc. | Protected encapsulation of catalytic layer for electroless copper interconnect |
JP3998455B2 (ja) * | 2001-11-02 | 2007-10-24 | 株式会社荏原製作所 | 無電解めっき装置及び無電解めっき方法 |
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JP2004031586A (ja) * | 2002-06-25 | 2004-01-29 | Sony Corp | 半導体装置の製造方法 |
JP4401912B2 (ja) * | 2003-10-17 | 2010-01-20 | 学校法人早稲田大学 | 半導体多層配線板の形成方法 |
JP4559936B2 (ja) * | 2004-10-21 | 2010-10-13 | アルプス電気株式会社 | 無電解めっき方法およびこの方法を用いた回路形成方法 |
JP5076482B2 (ja) * | 2006-01-20 | 2012-11-21 | 富士通セミコンダクター株式会社 | 半導体装置の製造方法 |
KR100856873B1 (ko) * | 2007-01-05 | 2008-09-04 | 연세대학교 산학협력단 | 무전해도금용 촉매활성 방법 |
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US20110168430A1 (en) * | 2008-09-11 | 2011-07-14 | Takuya Hata | Method of forming metal wiring and electronic part including metal wiring |
KR101078738B1 (ko) * | 2009-09-08 | 2011-11-02 | 한양대학교 산학협력단 | 반도체 소자의 구리배선 및 그 형성방법 |
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US20160013101A1 (en) | 2016-01-14 |
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